Manufacture of azo dyestuffs and process of dyeing textile materials therewith



30 p by the reaction Patented Feb. 27, .1 940 MANUFACTURE raoonss or on: amps 'rnaaawrrn HansKnikallaand 'r OFFICE mo TEXTILE MATE- Woligang Alt, Ludwigshai'enon-the-Rhlne, Germany, aaaignors to General Aniline & Film Delaware Corporation, a corporation of rial No. 177,916. In 1936 7 Claims.

( The present invention relates to azo dyestufis, a process of producing same and a process of dyeing textile materials therewith.

We have found that azo dyestufis having valuable properties are obtained by causing diazo compounds of aromatic amines to react with such ortho-hyclroxy-aryl carboxylic acid arylides, capable of coupling, as are substituted at least once in an aryl nucleus of the arylide radicle by 10 a group of the formula OR, in which R is an aliphatic radicle having at least group.

Suitable ortho-hydroxycarboxylic acid arylides are obtained, for example, by causing the 1'01- lowing ortho-hydroxycarboxylic acids or their chlorides -or esters to react with aromatic amines:-1-hydroxybenzene-2-carboxylic acid, methyl-l-hydroxybenzene 2 carboxylic acids, 2-hydroxynaphthalene-3-carboxylic acid, 2-hydroxy-6-methoxynaphthalene-3-carboxylic acid,

2-hydroxyanthracene-3-carboxylic acid, 3-hydroxydipheny'lene-oxide-2-carb0xylic acid, Ii-hydroxytriphenylene-(i-carboxylic acid, 2-hydroxycarbazole-3-carboxylic acid and 7.8-benzocarbazole-Bz.3-hydroxy-2carboxylic .acid.

.As amines suitable for the preparation of the arylides there may be mentioned, for example, the hydroxyalkoxyaminobenzenes and their substitution products, such as are obtained, for exoi. equimolecular amounts one tree hydroxyl of.nitrophenols with chlorhydrin, epichlorhydrin, propylene oxide, or butylene dioxideand subsequent reduction. Instead of hydroxyalkoxyaminobenzenes, the corresponding hydroxyalkoxy compounds derived i'rom aminonaphthalenes, -diphenyls, -stilbenes and other polynuclear aromatic amines may also be used, in particular amines which contain two or more hvdroxyalkoxy groups,

40 4.4'-diamino-3.3' di omega hydroxvethoxydiphenyl. For the preparation of the hydroxycarboxylic acid arylides serving as azo components, there may also be mentoned as being especially suitable the amines prepared from the addition compounds of two, three or more molecules of an alkylene oxide with nitrophenols, nitronaphthols and the like, as, for example, diethyleneglycol-mono-ortho-, -meta.- or -paraaminophenyl ether or the amine or the formula:

I ENQQNH; HOOHiCHIOOHiOH) OHIOHQOOHIOHIOH which may be reacted with two molecular pro- 85 portions of an ortho-hydroxyar'ylcarboxylic acid.

As diazo components accordingto this invention there may be mentioned the mines usually ethylene oxide, ethyleneas, for example.

Germany December 29,

employed in the preparation of azo dyestufis, such as aniline, nitroaminobenzenes, nitroaminophenols aminodiphenylamines, aminoazoben-- or on the fiber. They may serve for dyeing wool,-

cotton and viscose artificial silk. The dyestuffs are especially suitable for dyeing mixed fabrics of wool and viscose artificial silk because'the azo components, especially when they contain two or more hydroxyl groups in the alkoxy groups of the arylideradicle, have a good solubility even in slightly alkaline or even in'neutral media. When. preparing the dyestufis on the fiber, it is preferable to bottom the fabric to be dyed with the hydroxycarboxylic acid arylide and then to treat it, with a diazonium solution.

It is already known to prepare dyestufis by coupling diazotized aromatic amines with hydroxyarylcarboxylic' arylides containing in the arylide radicle a hydroxyalkyl ether'group. The new dyestuffs, when prepared in substance, are considerably faster to mineral and vegetable oils than the known dyestufis. When preparing the dyestufis on the fiber, the present process is distinguished from the known one in that the coupling components used'may be dissolved more easily, faster and while applying less amounts of alkali than the coupling components used in the known process.

The following examples will further illustrate how our invention may be carried out in practice but the invention not restricted to these examples.

Example 1 3 grams of the hydroxycarboxylic acid arylide of the formula:

are dissolved in a small amount-oi hot alcohol and the solution added in small portions to a solution, heated to C., or 5 grams or the addition compound of 15 molecular proportions of ethylene oxide to octadecyl alcohol in 1 liter of water. At the same time such an amount of dilute caustic soda solution is added that any milky cloudiness occurring is converted into a pure yellow solution. Alter the whole has been added, the solution has a weak alkaline reaction to phenolphthalein. The whole is then rapidly cooled to 60 C. and a fabric of cotton or viscose artificial silk or a previously wetted mixed fabric of 70 per cent of wool and 30 per cent of viscose artificial silk is introduced into the solution and moved therein for half an hour. After squeezing off, the fabric is treated for half an hour with a neutral solution of diazotized 4-chlor-2-nitro-laminobenzene, a brilliant red dyestufi thus being obtained on the fiber. The fabric is then treated with a soap solution at the boiling point or, in the case of the mixed fabric, advantageously at 70 C. fastness properties.

The dyeings have excellent Similar dyeings are obtained by using hydroxycarboxylic acid arylides containing the hydroxyethyloxy group in the metaor para-positions to the amide group instead of in the ortho-position.

Example 2 4 grams of the hydroxycarboxylic acid arylide having the formula: on

- no omo'mo omomo are triturated with a small amount of alcohol and poured into a solution, heated to C., of 25' cubic centimeters of normal sodium carbonatev solution in 1 liter of water. The clear, pale yellow solution is cooled rapidly to 30 C. and a fabric of wool or cotton or a mixed fabric of '70 per cent of wool and 30 per cent of viscose artificial silk is introduced into the solution and moved therein.

for half an hour. After squeezing off, the fabric is treated for half an hour at room temperature with a neutral solution of diaz'otized 4-amino- 4-methoxy-diphenylamine. Adark blue dyestufi is obtained on the fiber. After treatment with soap, the dyeings have excellent fastness properties.

Example 3 having the formula:

on v no 0a CONH-QQNHCQ noomomo I OCHsCHzOH excellent iastness properties after alkaline soap ing at the boiling point.

Very fast dyestuffs are also obtained by using as the azo component, instead of the said hydroxycarboxylic acid arylide, those containing the radicle instead of the radicle womenion.

- 3-methoxydiphenylamine, a

having the formula:

properties after a soap treatment at 70. C.

- Example 4 I 1 gram of the hydroxycarboxylic acid arylide of the formula:v

i CH

' comanoomomo is'dissolved in a small amount of warm water while adding'2 cubic centimeters of caustic soda solution of 40 Baum strength, the solution then being made up to 1 liter with water. A fabric of cotton or viscose artificial silk is moved in the solution for half an hour. After squeezing on, it

is treated with a solution of diazotized 4-aminogreen dyestuff thus being obtained. The dyeings have excellent fastness properties after alkaline soaping at the boil ing point.

' Example 5 5 grams a the hydroxycarboxylic acid arylide on v o omomon com:

.noomomo j are dissolved in a small amount taken by the addition of a weakbase (such as ammonia, sodium carbonate or aliphatic amines) that no cloudiness occurs. A mixed fabric of 70 per cent of wool and 30 per cent of viscose artificial silk is moved in the solution for half an hour. After squeezing oil, the fabric is treated for half an hour with a neutral solution of diazotized of alcohol and the solution added to a liter of water, care being.

5-nitro-2-amino-l-methyibenzene, a red dyestufi thus being formed. The dyeing has good iastness Similar dyestuffs are obtained byvuslng an arylide containing two radicles of the formula -'O(CHiCHz;O) 4CHiCH2OH it is possible to carry .hy-. droxycarboxylic acid arylides containing the I .radicle 2 grams of the hydroxycarboxylic acid arylide I instead of the radicle -ocracrnon. By using out the preparation of the azo dyestufi in neutral solution. I v

The preparation of the 'dyestufi may. also be efiected by dissolving the sodium salt of the hydroxycar'boxylic acid arylide in water with the addition of 'a small amount of ammonia- The said solutions react neutral to phenolphthalein.

Example 6 An ice-cooled tetrazo solution 0.5 .molecular proportion of 4.4'-diamino-3-3'- dimethoxydiphenyl is allowed to. fiow at from 0 to 10 C. into a solution'of 1 molecular proportion of the hydroxycarboxylic, acid arylide of the formula:

CONE

v 1 molecularproportion oi sodium hydroxide derived from water. The resulting disazo dyestufl separates as 1.5 molecular proportions of sodium carbonate in a blue water-insoluble powder. After stirring for 12 hours and heating to 60 C. for an hour, the dyestufl is filtered off by suction, washed with warm sodium carbonate solution and water and dried in vacuoat 40 C. The dyestuif is entirely insoluble in water and hydrocarbons and is eminently suitable as-a pigment dyestuff. 1

If, under the samev conditions, 1 molecular proportion 'of .the arylide of the formula:

/OH I 7 coNrr nocnicnio be reacted with the difz'o compound derived from Eatample 7 6 grams of the arylide corresponding to the formula 0n coma? onion are mixed with 30 com. of alcohol, 18 com. of a 25 per cent aqueous ammonia solution, and 6 grams of the addition product of '20 molecular proportions of ethylene oxide to 1 molecular pro portion of an oleyl alcohol. The whole is slightly heated, stirred into water of C., the solution being made up to 1 liter, with water.

A fabric of 70 per cent of wool and 30 per cent of viscose artificial silk-is moved in this solution for half an hour at 25. 0., after having added thereto 10 grams of common salt. After squeezing oil, the fabric "is moved for half an hour at room temperature in a neutral solution of diazotized 4-amino-4'-methoxydiphenylamine. 1 After quick rinsing, the fabric is treatedfor half an hour at C. in an'aqueous bath, containing 8 grams of Marseilles soap per liter. ,Blue dyeings are obtained'which are excellently fast to light and show good fastness to washing and iulli'ng.

Example 8 5 grams of the arylide corresponding to the formula HOE HzOH

formula and 50 com. 01' a 25 per cent aqueous ammonia solution,the solution being made up to 1 liter with water, while simultaneously adding a small amount 01 sulflte cellulose waste liquor. A viscose fabric is treated in this bath for half an hour at 50 (3., squeezed ofl and moved for half an hour in a neutral solution of diazotized 2.5- dic'hlor-l-aminobenzene. Very fast brown dyeings are thus obtained.

What we claim is:

1. Azo dyestuffs corresponding to the general wherein A1, stands for an aromatic radicle, A2

for the radicle of an ortho-hydroxyaryl carboxylic acid amide, m; for a whole number up to i 2, and D for an aryl radicle substituted at least once in the aryl nucleus by formula a group of the i i 0-R--0.- L p a. wherein R represents a low molecular alkylene radicle and n a whole number.

2. Azo dyestuffs corresponding to the formula wherein A1 stands for an ,i radicle, m for a whole number up to 2', and D for an aryl radicle substituted at-least once in. the aryl nucleus by a roup of the formula F "l 0-R-0-H I B- in wherein R represents a low molecular almlene, radicle and n a whole nben.

3. Azo dyestuffs corresponding to the general Iformula' AN=NB wherein a stands for an, aromatic radicle free from water-soluhilizing groups, wherein B stands for the radicle of a 2.3-hydroxynaphth0ic acid anilide substituted at least once in the benzene nucleus of the aniiide radicle by a group of the formula wherein "R represents a low molecular allene.

DOHQCBIOH 5. 'I'he azo dyestufl. of the formula .ONHPQNHQ. noomoln K ooniomon' s. The azo (1mm of the oi-mule. me material containing both wool and vlacoseartificial silk which comprises applying to said -C -N=N material an ortho-lwdroxyaryl carboxylicarylide v capable of being'coupled and being substituted- 5 at least once in an aryl nucleus of the mlide F radicle by a. group of the formula o n-o -n ONE L I m in which R. represents a low molecular alkylene radicle and n a. whole number; converting said 1 v 53, mum into we dyestufls by treatment with a diamtized aromatic amines.

I HgOH m All f 15 '1. A process of producing mt m on texwonmma ALT. ll 

